CN105646090B - Agricultural organic waste is modified as release and release control fertilizer of degradable membrane and preparation method thereof - Google Patents
Agricultural organic waste is modified as release and release control fertilizer of degradable membrane and preparation method thereof Download PDFInfo
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- CN105646090B CN105646090B CN201610124899.7A CN201610124899A CN105646090B CN 105646090 B CN105646090 B CN 105646090B CN 201610124899 A CN201610124899 A CN 201610124899A CN 105646090 B CN105646090 B CN 105646090B
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G5/00—Fertilisers characterised by their form
- C05G5/30—Layered or coated, e.g. dust-preventing coatings
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C5/00—Fertilisers containing other nitrates
- C05C5/02—Fertilisers containing other nitrates containing sodium or potassium nitrate
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C9/00—Fertilisers containing urea or urea compounds
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
- C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F5/00—Fertilisers from distillery wastes, molasses, vinasses, sugar plant or similar wastes or residues, e.g. from waste originating from industrial processing of raw material of agricultural origin or derived products thereof
- C05F5/002—Solid waste from mechanical processing of material, e.g. seed coats, olive pits, almond shells, fruit residue, rice hulls
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Abstract
The present invention relates to the release and release control fertilizers and preparation method thereof that a kind of agricultural organic waste is modified as degradable membrane；It is to be uniformly mixed agricultural organic waste, liquefier, catalyst to liquefy to be modified to obtain film-coated controlled release fertilizer as coated fertilizer；Film-coated controlled release fertilizer produced by the invention has good accurate controlled release properties, by adjusting membrane wrapping thickness, the control of product nutrient controlled release phase can be made to differ at 1-6 months.Meanwhile the product of invention production use agricultural organic waste for raw material, this raw material are reproducible resources, be manured into soil in can also degrade, for environmentally friendly material.This product uses novel renewable coated fertilizer, so that coated fertilizer is got rid of the dependence to chemical materials such as petroleum, reduces the waste of resource, realize sustainable development.Raw material sources of the invention are extensive, thus produce product price is cheap, preparation process is easy, to be mass produced and popularization is laid a good foundation.
Description
(1) technical field
The present invention relates to the release and release control fertilizers and preparation method thereof that a kind of agricultural organic waste is modified as degradable membrane, belong to
Release and release control fertilizer production field.
(2) background technique
Film-coated controlled release fertilizer is a kind of intelligent fertilizer that can accurately control Nutrient Release.It is by fertilizer table
Face forms the hypotonic permeable membrane of one layer of polymeric, thus can control water and enter fertilizer core and nutrient solution out of film to outside expansion
Scattered speed.Therefore, the property of the thickness of adjustable film and film reaches different controlled-release effects, is allowed to adapt to Different Crop
Nutrient demand characteristic, with achieve the purpose that improve fertilizer efficiency.The invention application of coated fertilizer not only substantially increases fertilizer utilization
Rate reduces the waste of fertilizer, also reduces pollution of the fertilizer to the water bodys such as underground water, river and environment, and reduce labor
Employ work.
Currently, coated fertilizer has various coating formulas and a variety of coating process.Studying both at home and abroad more has
The coated fertilizer of solvent type, with Japanese " Meister " and " Osmocote " in the U.S. for representative.These fertilizer are by coating material
Material is first dissolved in organic solvent, is then wrapped in fertilizer surface by fluidized-bed process, finally recycles organic solvent.This life
Membrane material can be uniformly wrapped in fertilizer surface by production. art, but this process energy consumption is high, and process is complicated, and organic solvent has mostly
Compared with high toxicity and cost recovery it is higher.Therefore, the coated fertilizer produced using this technique is often at high price, is only limitted to limited
Industrial crops and flowers use, it is difficult to promote.
There are also one is directly in the production technology of fertilizer surface reaction film forming.The material that this technique uses mainly has epoxy
Resin, polyurethane resin etc..This technique usually uses liquid film material and curing agent and directly reacts in fertilizer surface into control
Release film.This technological operation is simple, and the film-forming time is shorter, therefore, can promote the use of on a large scale.But due to this film
The primary raw material of material derives from petrochemicals, and petrochemicals cost is also higher and petroleum is non-renewable money
Source, therefore it is unfavorable for the sustainable development of release and release control fertilizer industry.In addition, Chinese patent is " using agricultural crop straw as degradable membrane
Film-coated controlled release fertilizer and its production method " (patent No. 201210261735.0, publication No. CN102795924A) discloses one kind
It is the coated fertilizer of degradable membrane material using agricultural stalk liquefaction, but its liquefied organic waste is single stalk
Or other organic matters, the fiber content of every kind of single organic matter are different from, this causes liquefaction result less desirable.In addition,
Its liquefied temperature is generally higher, can reach 150 DEG C even 200 DEG C, and the time of continuous high temperature is long, can reach 1.5h even
2h causes energy consumption high, and prolonged pyroreaction be easy to cause charing.Moreover, this membrane material contains more water suction group,
Though the production of coated fertilizer can be used for, membrane material controlled-release effect is undesirable, to reach preferable nutrient release characteristics, it is necessary to add
Big membrane material dosage causes production cost higher moreover, the temperature of coating process is also very high, is difficult big face on field crop again
Product is promoted.
(3) summary of the invention
To solve the above problems, the present invention provides the release and release control fertilizers that a kind of agricultural organic waste is modified as degradable membrane
And preparation method thereof, be it is a kind of using organic-silicon-modified agricultural organic waste as the film-coated controlled release fertilizer of degradable membrane material and its
Production method.This method can solve the single problem of stalk ingredient using two or more organic waste.This method
Liquefaction reaction selects novel liquefier cyclohexanol, n-butanol and p-methyl phenol, in liquefaction process, is quickly ramped up to high temperature 150
DEG C heating 10min, is then down to 110-120 DEG C of maintenances 10-20min of medium temperature, be finally down to 100 DEG C of low temperature lasting 10min up to
Reaction terminates, and is cooled to room temperature.This liquefaction process, temperature needed for the liquefaction process than other methods is low, and continuous high temperature is only
For 10min, high-temperature time is short, greatly reduces energy consumption, and effectively prevent the charing of organic matter, the time of reaction is also than it
He reduces 0.5-1.5h at method, further reduced energy consumption.Change in addition, this method is added on the basis of degradable membrane material
Property agent organosilicon, from curing agent in different ratios simultaneously in fertilizer surface film-forming, the addition of modifying agent organosilicon increases
The hydrophobic performance of membrane material, substantially prolongs fertilizer releasing period, improves the controlled-release effect of coated fertilizer.In addition, with direct benefit
It is compared with the method that liquefaction of corn straw object is coated fertilizer, due to the introducing of organic silicon hydrophobic group, greatly reduces membrane material
Dosage, and controlled-release effect is more preferable.Since organosilicon modifier additional amount is seldom, and price is also cheap, therefore, the present invention and its production
Product preparation method has the features such as at low cost, resource regeneration, degradable, simple process, less energy consumption, is conducive to be widely popularized and answer
With.
A kind of agricultural organic waste is modified as the release and release control fertilizer of degradable membrane, and preparation method is to crush 20-30 parts
Agricultural organic waste, 100 parts of liquefiers, 3-5 parts of catalyst are uniformly mixed, be brought rapidly up to reacting 10min at 150 DEG C,
It is down to 110-120 DEG C of reaction 10-20min, then is cooled to 100 DEG C of reaction 10min reaction was completed, can be obtained after being cooled to room temperature
Liquefaction products；Fertilizer in seed-coating machine is preheating to 30-40 DEG C, then mixes liquefaction products, modifying agent and curing agent in proportion
It closes and uniformly sprays or be added directly into seed-coating machine as coated fertilizer, film-forming obtains film-coated controlled release fertilizer；The fertilizer
Material is common urea, compound fertilizer, monoammonium phosphate, Diammonium phosphate (DAP), potassium sulfate, potassium chloride or the potassium nitrate of diameter 2-5mm.
The agricultural organic waste is wheat stalk, peanut shell, sawdust, corncob, cotton stalk and/or cotton boll hull
Two or more mixture in；Preferably, the agricultural organic waste is wheat stalk, peanut shell, cotton boll
Shell according to weight ratio 1:1:1 mixture.
The liquefier be two kinds or two kinds in cyclohexanol and n-butanol, p-methyl phenol or ring carbon vinyl acetate with
On mixture；It must be added to cyclohexanol in each liquefier combination；Preferably, the liquefier is cyclohexanol, to methylbenzene
The mixture that phenol, ring carbon vinyl acetate are 1:1:1 according to weight ratio.
The catalyst is the mixture of both the concentrated sulfuric acid and platinum-tungsten alloys catalyst；The preferred concentrated sulfuric acid and platinum tungsten close
Golden mixed catalyst according to weight ratio 1:1-2 mixture.
The modifying agent is hexamethyl cyclotrisiloxane, γ-glycidoxypropyl group trimethyl silane or dimethyl-silicon
One or two kinds of mixtures of oxygen alkane.Preferably, the modifying agent is hexamethyl cyclotrisiloxane, γ-glycidoxy
The mixture that oxypropyl trimethyl silane, dimethyl siloxane are 1:1:1 according to weight ratio.
The curing agent is isophorone diisocyanate, hexylidene diisocyanate, trans cyclohexane diisocyanate
The mixture of one or more of ester, methyl diphenylene diisocyanate.
The liquefaction products, modifying agent, curing agent account for respectively the coated fertilizer weight ratio 20-60%, 5-15%,
30-65%, it is 100% that the liquefaction products, modifying agent and curing agent, which account for the sum of weight percent of coated fertilizer,；It is sprayed on fertilizer
The coated fertilizer of material particle surface accounts for the 3-10% of release and release control fertilizer total weight.
The method is characterized in that
Main points first is that: liquefier, agricultural organic waste, catalyst ratio certain in sequence are added to instead
It answers in kettle, i.e., first liquefier is added in reaction kettle, and open heating and stirring, then add organic waste powder,
Catalyst is added, and reaction process is rapidly heated first to 150 DEG C of high temperature and heats 10 minutes, then maintains medium temperature 110-
120 DEG C 10-20 minutes, finally 100 DEG C of low temperature react 10 minutes.The time lower than other methods temperature 50 of entire reaction process
DEG C -100 DEG C, time short 0.5-1.5h reduces energy consumption.
Main points second is that: this product preparation process is simple, and film forming is reacted directly in rotary drum, and required energy consumption is small, instead
Short one minute i.e. curable film-forming under the conditions of 30-40 DEG C not only reduces reaction temperature than other methods between seasonable, but also reduces
Reaction time.
Third key point is: on the basis of calculating accurate proportion, the addition of organosilicon increases the hydrophobicity of membrane material
Can, achieve the purpose that improve film-coated controlled release fertilizer controlled-release effect, it is reachable using the film-coated controlled release fertilizer controlled release phase produced by the invention
It was differed by 1-12 months, and the same controlled release phase, modified coated fertilizer reduces the left side 30-50% than unmodified coated fertilizer
Your other product controlled release periods of the controlled release period of coated fertilizer this product of right identical weight increase 30-90%.
Advantages of the present invention:
1. there is waste as raw material using typical agricultural, it is basic containing various biological organic materials have been covered, it takes full advantage of
Discarded renewable resource not only reduces the wasting of resources and the pollution to environment, and greatly reduces cost, reduces pair
The dependence of petrochemicals, realizes sustainable development.
2. the condensing temperature chosen is relatively low, the time of liquefaction reaction is lower, greatly reduces energy consumption, reduces cost.
3. the coating process taken is simple, curing time is fast, suitable for mass production.
4. film-coated controlled release fertilizer residual film produced by the invention can degrade and containing certain organic nutrient substance, decompose
After can give crop provide nutrition.
5. film-coated controlled release fertilizer controlled-release effect is good, the controlled release phase at 1-12 months or so, can meet difference as required
The regulation of fertilizer requirement of crop.
(4) Detailed description of the invention
The organic-silicon-modified agricultural organic waste of Fig. 1 is the film-coated controlled release fertilizer production technological process of degradative membrane.
In figure: 1, being first put into seed-coating machine and be preheating to 30-40 DEG C urea or other fertiliser granulates；2, by the agriculture of crushing
Industry organic waste powder is added to react according to the method described above in reaction kettle by a certain percentage and be liquefied with liquefier, catalyst
Product；3, curing agent isocyanates and liquefaction products are sprayed simultaneously or are added in seed-coating machine；4, by a certain amount of modifying agent
It sprays or is added in seed-coating machine；5, coating liquefaction products, curing agent, liquefier are directly reacted in fertiliser granulates surface is solidified into
Film；6, fertilizer is taken out from seed-coating machine, is put into cooler, and room temperature is then allowed to cool；7, weigh fertilizer after cooling,
Measurement, packaging, storage.
(5) specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The material can be gotten from open business unless otherwise instructed.Institute
The agricultural organic waste powder diameter stated is 20-60 mesh, uses preceding drying 24 hours at 105 DEG C.
Embodiment 1:
After 4.4kg cyclohexanol, p-methyl phenol, ring carbon vinyl acetate are mixed according to weight ratio for 1:1:1 ratio, it is added
It into the double-layer glass reaction kettle with blender and heating device, begins to warm up and stirs, then slowly add wheat stalk, flower
After being heated to 145 DEG C, the concentrated sulfuric acid and platinum-tungsten alloys catalyst (weight is added in raw shell, cotton boll hull powder (weight ratio 1:1:1) 1kg
Than 1:1) 0.14kg, reacts 10 minutes at 145-150 DEG C, reacts 15 minutes at 120 DEG C, be then cooled to 100 DEG C of reactions
Reaction was completed after ten minutes, is cooled to room temperature, and obtains liquefaction products.The granular urea of 500kg3-5mm is added to seed-coating machine
In pot body, it is preheating to 30-40 DEG C, then by 3kg liquefaction products, 1.5kg isophorone diisocyanate, the pregnancy basic ring of 1kg
Trisiloxanes, γ-glycidoxypropyl group trimethyl silane, dimethyl siloxane according to weight ratio be 1:1:1 after mixing
It is added in seed-coating machine, can be repeated in fertiliser granulates surface film-forming according to the thickness of required coating after 1-2 minutes
This process until the amount of coated fertilizer is added needed for reaching oneself, can pack storage after finally fertilizer being waited to be cooled to room temperature
Hiding.For example, the coated fertilizer that above-mentioned coating process is repeated 5 times resulting film-coated controlled release fertilizer accounts about the 5% of fertilizer gross weight, this
For fertilizer in 25 DEG C of water or soil, nutrient controlled release period is about 120 days, increases controlled release period compared with unmodified release and release control fertilizer
90% or so.
Embodiment 2:
After 3.2kg cyclohexanol, p-methyl phenol, ring carbon vinyl acetate are mixed according to the ratio that weight ratio is 1:1:1, add
Enter into the double-layer glass reaction kettle with blender and heating device, begins to warm up and stir, be then slowly added into Wheat Straw
After being heated to 145 DEG C, the concentrated sulfuric acid and platinum-tungsten alloys catalyst (weight ratio is added in stalk, peanut shell powder (weight ratio 1:1) 0.8kg
1:1) 0.12kg reacts 10 minutes at 145-150 DEG C, reacts 20 minutes at 120 DEG C, is then cooled to 100 DEG C of reactions 10
Reaction was completed after minute, is cooled to room temperature, obtains liquefaction products.The granular urea of 500kg3-5mm is added to coating machine boiler
In vivo, it is preheating to 30-40 DEG C, then by 3kg liquefaction products, 1.5kg hexylidene diisocyanate, three silicon of 0.5kg pregnancy basic ring
Oxygen alkane is added in seed-coating machine after mixing, can repeat 5 in fertiliser granulates surface film-forming, this process after 1-2 minutes
Secondary, finally equal fertilizer can pack storage after being cooled to room temperature.It is total that the membrane material of resulting film-coated controlled release fertilizer accounts about fertilizer
The 5% of weight, for this fertilizer in 25 DEG C of water or soil, nutrient controlled release period is about 90 days, is increased compared with unmodified release and release control fertilizer
Controlled release period 30% or so.
Embodiment 3:
After 3.2kg cyclohexanol, p-methyl phenol, ring carbon vinyl acetate are mixed according to the ratio that weight ratio is 1:1:1, add
Enter into the double-layer glass reaction kettle with blender and heating device, begins to warm up and stir, be then slowly added into Wheat Straw
After being heated to 145 DEG C, the concentrated sulfuric acid and platinum tungsten is added according to the weight ratio mixed-powder 0.8kg of 1:1:1 in stalk, peanut shell, cotton boll hull
Alloy catalyst (weight ratio 1:2) 0.12kg reacts 10 minutes at 145-150 DEG C, reacts 20 minutes at 120 DEG C, then
Being cooled to 100 DEG C of reactions, reaction was completed after ten minutes, is cooled to room temperature, obtains liquefaction products.By the bulky grain of 500kg3-5mm
Urea is added in coating machine boiler body, is preheating to 30-40 DEG C, then by 3kg liquefaction products, 1.5g trans cyclohexane diisocyanate
Ester, 1kg dimethyl siloxane are added in seed-coating machine after mixing, can be solidified into fertiliser granulates surface after 1-2 minutes
Film, this process are repeated 7 times, and finally equal fertilizer can pack storage after being cooled to room temperature.The membrane material of resulting film-coated controlled release fertilizer
Material accounts about the 7% of fertilizer gross weight, this fertilizer is in 25 DEG C of water or soil, and nutrient controlled release period is about 210 days, compared with unmodified
Release and release control fertilizer increase controlled release period 80% or so.
Embodiment 4:
After mixing 3.2kg cyclohexanol, ring carbon vinyl acetate by weight the ratio of 1:1, it is added to blender
It in the double-layer glass reaction kettle of heating device, begins to warm up and stirs, be then slowly added into wheat stalk, peanut shell, cotton boll
Shell according to 1:1:1 weight ratio mixed-powder 0.8kg.After being heated to 145 DEG C, the concentrated sulfuric acid and platinum-tungsten alloys catalyst (weight is added
Amount is than 1:1.5) 0.12kg, reacts 10 minutes at 145-150 DEG C, reacts 15 minutes at 120 DEG C, be then cooled to 100 DEG C
Reaction was completed after ten minutes for reaction, is cooled to room temperature, obtains liquefaction products.The granular urea of 500kg3-5mm is added to packet
In clothing machine pot body, it is preheating to 30-40 DEG C, then by 3kg liquefaction products, 1.5kg methyl diphenylene diisocyanate, the end 0.5kg
Hydroxyl dimethyl silicone polymer, γ-glycidoxypropyl group trimethyl silane, dimethyl siloxane (weight ratio 1:1:1) mixing
It is added in seed-coating machine after uniformly, can be repeated 5 times in fertiliser granulates surface film-forming, this process after 1-2 minutes, finally etc.
Fertilizer can pack storage after being cooled to room temperature.The membrane material of resulting film-coated controlled release fertilizer accounts about the 5% of fertilizer gross weight, this
For fertilizer in 25 DEG C of water or soil, nutrient controlled release period is about 180 days, increases controlled release period compared with unmodified release and release control fertilizer
40% or so.
Claims (5)
1. the release and release control fertilizer that a kind of agricultural organic waste is modified as degradable membrane, it is characterised in that obtained by following preparation method
It arrives:
The agricultural organic waste that 20-30 parts are crushed, 100 parts of liquefiers, 3-5 part catalyst are uniformly mixed, be brought rapidly up to
10min is reacted at 150 DEG C, is down to 110-120 DEG C of reaction 10-20min, then is cooled to 100 DEG C of reaction 10min reaction was completed, it is cold
But to liquefaction products can be obtained after room temperature；Fertilizer in seed-coating machine is preheating to 30-40 DEG C, then by liquefaction products, modifying agent
It is mixed in proportion with curing agent and is sprayed as coated fertilizer or be added directly into fertiliser granulates surface in seed-coating machine, solidified
Film-coated controlled release fertilizer can be made after film forming；
The fertilizer is common urea, compound fertilizer, monoammonium phosphate, Diammonium phosphate (DAP), potassium sulfate, potassium chloride or the nitre of diameter 2-5mm
Sour potassium；
The agricultural organic waste is in wheat stalk, peanut shell, sawdust, corncob, cotton stalk and/or cotton boll hull
Two or more mixture；
The liquefier is two or more in cyclohexanol and n-butanol, p-methyl phenol or ring carbon vinyl acetate
Mixture；It must be added to cyclohexanol in each liquefier combination；
The catalyst is the mixture of both the concentrated sulfuric acid and platinum-tungsten alloys catalyst；
The modifying agent is hexamethyl cyclotrisiloxane, γ-glycidoxypropyl group trimethyl silane or dimethyl siloxane
One or two kinds of mixtures；
The curing agent is isophorone diisocyanate, hexylidene diisocyanate, trans cyclohexane diisocyanate, two
The mixture of one or more of methylenebis phenyl isocyanate；
The liquefaction products, modifying agent, curing agent account for 20-60%, 5-15%, 30- of the weight ratio of the coated fertilizer respectively
65%, it is 100% that the liquefaction products, modifying agent and curing agent, which account for the sum of weight percent of coated fertilizer,；It is sprayed on fertilizer
The coated fertilizer on grain surface accounts for the 3-10% of release and release control fertilizer total weight ratio.
2. the release and release control fertilizer that a kind of agricultural organic waste as described in claim 1 is modified as degradable membrane, it is characterised in that
The agricultural organic waste is wheat stalk, peanut shell, cotton boll hull according to weight ratio 1:1:1 mixing.
3. the release and release control fertilizer that a kind of agricultural organic waste as described in claim 1 is modified as degradable membrane, it is characterised in that
The liquefier be cyclohexanol, p-methyl phenol, ring carbon vinyl acetate according to weight ratio be 1:1:1 mixing.
4. the release and release control fertilizer that a kind of agricultural organic waste as described in claim 1 is modified as degradable membrane, it is characterised in that
The modifying agent is hexamethyl cyclotrisiloxane, γ-glycidoxypropyl group trimethyl silane, dimethyl siloxane according to weight
Amount is than being that 1:1:1 is mixed.
5. the release and release control fertilizer that a kind of agricultural organic waste as described in claim 1 is modified as degradable membrane, it is characterised in that
The catalyst is the mixture of the concentrated sulfuric acid and platinum-tungsten alloys mixed catalyst according to weight ratio 1:1-2.
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| CN113416106B (en) * | 2021-06-21 | 2023-03-14 | 山东农业大学 | Preparation method of liquefied bio-based coated controlled release material |
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| CN102795924B (en) * | 2012-07-26 | 2013-12-04 | 山东农业大学 | Coated controlled-release fertilizer using crop straws as degradable film and production method of fertilizer |
| CN103013552B (en) * | 2012-12-17 | 2015-07-22 | 常州大学 | Method for preparing biological oil by liquefying biomass under atmospheric pressure by using solid acid catalyst |
| CN103242086B (en) * | 2013-01-17 | 2014-06-11 | 山东农业大学 | Starch-liquefying modified thermosetting resin film-coated controlled release fertilizer and preparation method thereof |
| CN103964970B (en) * | 2014-05-28 | 2015-07-08 | 山东农业大学 | Waste paper modified coated control release fertilizer and preparation method thereof |
| CN105016874B (en) * | 2015-07-15 | 2018-03-02 | 北京市农林科学院 | A kind of liquefaction of corn straw coating liquid and preparation method and application |
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Application publication date: 20160608 Assignee: KINGENTA ECOLOGICAL ENGINEERING GROUP Co.,Ltd. Assignor: Shandong Agricultural University Contract record no.: X2021370000037 Denomination of invention: Controlled release fertilizer modified from agricultural organic waste into degradable membrane and its preparation method Granted publication date: 20190301 License type: Exclusive License Record date: 20211210 |